1,2,3-benzotrizine-4-ores

ABSTRACT

Benztriazinonylmethyl-organophosphoric esters of the formula Wherein R.sub.1 represents ethyl, propyl, isopropyl, n-butyl, ibutyl or sec. butyl and R.sub.2 represents methyl or ethyl, R.sub.3 represents hydrogen or methyl, a process for their manufacture and their use in pest control.

United States Paten Oswald et al.

Apr. 8, 1975 l,2,3-BENZOTRlZlNE-4-ORES [75] Inventors: Alexis A. Oswald,Mountainside;

Paul L. Valint, Woodbridge, both of NJ.

[73] Assignee: Ciba-Geigy AG, Basel. Switzerland [22] Filed: Dec. 26,1972 [21] Appl. No.: 318,128

[30] Foreign Application Priority Data Dec. 23. 1971 Switzerland18827/72 Nov. 22, 1972 Switzerland 17011/72 [52] US. Cl. 260/248 AS;424/249 [51] Int. Cl C07d 55/10 [58] Field of Search 260/248 AS [56]References Cited UNITED STATES PATENTS 3.131.186 4/1964 Magee et al.260/249.5 3.309.371 3/1967 Curry et al.... 260/248 X 3.420.829 1/1969Lorenz 260/248 Primary E.\'aminerJ0hn M. Ford Anorney, Agent, orFirmFrederick H. Rabin [57] ABSTRACTBenztriazinonylmethylorganophosphoric esters of the v formula Ro l l 4Claims, No Drawings 1 1 ,2 ,3-BENZOTRIZINE-4- ORES The present inventionrelates to benztriazinonylmethyl organophosphoric esters, a process fortheir In the formulae II to VI, R, to R have the meaning given for theformula I, X represents chlorine or bromine and M represents an alkalimetal, in particular sodium or potassium, ammonium or alkylammonium withmanufacture and their use in pest control. The benz- 5 l to 5 carbonatoms, R, is hydrogen, C, to C alkyl, C triazinonylmethylorganophosphoric esters have the to C alkyl thiocarbamate group. f0rmulaSuitable acid binding agents are: tertiary amines, e.g. trialkylamines,pyridine, dialkylanilines; inorganic 0 bases, such as hydrides,hydroxides; carbonates and bi o n 10 carbonates of alkali and alkalineearth metals. During R C the reactions it is sometimes necessary to usea catalyst,

e.g. copper or copper chloride. 1120 I I I Processes (a) to (d) can becarried out at normal R N pressure, at a temperature of 30C. to 120C.,and in Y N 15 solvents or diluents.

Examples of suitable solvents or diluents are: ethers (I) and etherealcompounds, such as diethyl ether, dipropyl ether, dioxan,tetrahydrofuran; amides, such as 70 N,N-dialkylated carboxylic amides;aliphatic, aromatic and halogenated hydrocarbons, in particular benzene,wherein R represents ethyl, ro yl, i l, b t 1, toluene, xylene,chloroform, chlorobenzene; nitriles, i-butyl or sec. butyl and Rrepresents methyl or ethyl, such as acetonitrile; dimethyl .sulphoxide;alcohols, R is hydrogen or methyl. Preferred compounds on acsuch asethanol; ket ones, such as acetone, ethyl methyl count of their actionare those of the formula I, wherein 25 ketone; and water. R representspropyl and R represents ethyl. The starting materials of the formula llto VII can be The compounds of the formula I can be manufacmanufacturedby methods analogous to those detured by the following methods. scribedin the literature.

0 a) R S ii ii P-SH xcn if acid binding R20 N agent I (II) N (III) 0 0II b) R1S ,c.

P-SM XCl-l N 1 R20 I '9 N (IV) N (III) 0 8 ll 0 H 0 l| c R4524 MS l| c RX P- S-CH- N P-- s- CH-N I 12 0 1 R 0 I l P- SH CE CH- N z 2 I I (VII)The insecticidal action of analogous compounds is disclosed in theliterature, but compared with these, the compounds of the formula I havesurprisingly a lesser toxicity to warm blooded animals and a distinctlymore powerful and long-lasting action against all development stages,such as eggs, larvae, nympjs, pupae and adults of insects, for exampleof insects of the families: Acrididae, Blattidae, Gryllidae,Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae,Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae,Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae,Curculionidae, Tineidae, Noctuidae, Lymantriidac, Pyralidae,Galleriidae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae,Trypetidae, Pulicidae.

The compounds of the formula I are also active against eggs, larvae andadults of representatives of the order Acarina, such as mites, spidermites and ticks, e.g. of the families Ixodidae, Argasidae, Tetranychidaeand Demanyssidae.

By addition of other insecticides and/or acaricides it is possible toimprove substantially the insecticidal or acaricidal action and to adaptit to given circumstances.

The following active substances are examples of suitable additives.

Organic Phosphorus Compounds Bis-0,0-diethylphosphoric acid anhydride(TEPP) Dimethyl-( 2,2,2-trichlorol -hydroxyethyl phosphonate(TRICHLORFON) 1 ,2-dibrom-2,2-dichloroethyldimethylphosphate (NALED)2,2-dichlorovinyldimethylphosphate VOS)2-methoxycarbamyl-1-methylvinyldimethylphosphate (MEVINPHOS) Dimethyll-methyl-2-( methylcarbamoyl vinylphosphate cis (MONOCROTOPHOS)3-(dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (DICROTOPHOS)2-chloro-2-diethylcarbamoyl- 1 -rnethylvinyldimethylphosphate(PHOSPHAMIDON) 0,0-diethyl-O( or S )-2-( ethylthio )-ethulthiophosphate(DEMETON) S-ethylthioethyl-0,0-dimethyl-dithiophosphate (THIOMETON)0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)0,0-diethyl-S-2-(ethylthio)ethyldithiophosphate (DISULFOTON)0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETON METHYL)0,0-dimethyl-S-l ,2-dicarbethoxyethy[dithiophosphate (MALATHlON)0,0,0,0-tetraethyl-S ,S '-methylene-bisdithiophosphate (ETHlON)O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N-formylcarbamoylmethyl)-dithiophosphate MOTHlON)0,0-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate (DIMETHOATE)0,0-dimethyl-O-p-nitrophenylthiophosphate RATl-llON-METHYL)0.0-diethyl-O-p-nitrophenylthiophosphate (PARA- THION)O-ethyl-O-p-nitrophenylphenylthiophosphate (EPN)0,0-dimethyl-O-(4-nitro-m-tolyl)thiophosphate (DICHLOR- (FOR- 4(FENITROTHION) 0,0-dimethyl-O-2,4,5-trichlorophenylthiophosphate(RONNEL) O-ethyl-O,2,4,5-trichlorophenylethylthiophosphate(TRlCHLORONATE) 0,0-dimethyl-O-2,5-dichloro-4-bromophenylthiophosphate(BROMOPHOS) 0,0-dimethyl-O-( 2,5-dichloro-4-iodophenyl thiophosphate(JODOFENPHOS) 4-tert.buty|-2-chIorophenyl-N-methyl-O-methylamidophosphate (CRUFOMATE) 0,0-dimethyl-O-(3-methyl-4-methylmercaptophenyl)thiophosphate (FENTH- ION)lsopropylamino-O-ethyl-O-(4-methylmercapto-3- methylphenyl)-phosphate0,0-diethyl-O-p-(methylsulphinyl)phenylthiophosphate (FENSULFOTHION)O-p-(dimethylsulphamido)phenyl-0,0-dimethylthiophosphate (FAMPHUR)0,0,0',O'-tetramethyl-0,0'-thiodi-p-phenylenethiophosphateO-ethyl-S-phenyl-ethyldithiophosphate0,0-dimethyl-O-(oz-methylben2yl-3-hydroxycrotonyl )phosphate2-chloro-l-(2,4-dichlorophenyl)vinyldiethylphosphate (CHLORFENVlNPl-IOS)l-chloro-l-(2,4,5-trichlorophenyl)vinyldimethylphosphateO-[Z-chloro-l-(2,5-dichlorophenyl)]vinyl-0,0-

diethylthiophosphate Phenylglyoxylonitriloxime-0,0-diethylthi0phosphate(PHOXIM)0,0-diethyl-O-(3-chloro-4-methyl-2-0xo-2-H-lbenzopyran-7-yl)-thiophosphate(COUMAPHOS) 2,3-p-dioxandithiol-S,S-bis(0,0-diethyldithiophosphate)(DIOXATHION) 5-[(6-chloro-2-oxo-3-benzoxazolinyl)methyl]0,0-

diethyldithio-phosphate (PHOSALONE) 2-(diethoxyphosphinylimino )-l,3-dithiolane 0,0-dimethyl-S-[Z-methoxyl ,3 ,4-thiadiazol-5-(4H)-onyl-(4)-methyl]dithiophosphate IO,O-dimethyl-S-phthalimidomethyl-dithiophosphate (lMIDAN)0,0-diethyl-O-( 3 ,5 ,6-trichloro-2-pyridyl )thiophosphate0,0-diethyl-O-Z-pyrazinylthiophosphate (Tl-[IONA- ZIN) 0,0-diethyl-O-(Z-isopropyl-4-methyl-6-pyrimidyl5-amino-bis(dimethylamido)phosphinyl-B-phenyll,2,4-triazole (TRlAMlPHOS)N-methyl-S-(0,0-dimethylthiolphosphoryl)-3-thiavaleramide (VAMIDOTHION)0,0-diethyl-O-[2-dimethylamino-4- methylpyrimidyl-( 6 ]-thiophosphateHYL) 0,0-dimethyl-S-(methylcarbamoylmethyl)- thiophosphate (OMETHOATE)O-ethyl-O-(8-quinolinyl)-phenylthiophosphonate (OXINOTHIOPHOS)O-methyl-S-methyl-amidothiophosphate TOR)O-methyl-O-(2,5-dichloro-4-bromophenyl)-benzothiophosphate (PHOSVEL)0,0,0,0-tetrapropyldithiophosphate3-(dimethoxyphosphinyloxy)-N-methyl-N-methoxycis-crotonamide0,0-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (ETHOATE-METHYL)0,0-diethyl-S-(N-isopropylcarbamoylmethyl)- dithiophosphate (PROTHOATE)S-N-( l-cyano-lmethylethyl)carbamoylmethyldiethylthiolphosphate(CYANTHOATE) S-( Z-acetamidoethyl )-0,0-dimethyldithiophosphatel-lexamethylphosphoric acid triamide (HEMPA) 0,0-dim ethyl-O-(2-chloro-4-nitrophenyl )thiopho sphate (DICAPTHON) 0,0-dimethylO-p-cyanophenyl (CYANOX) O-ethyl-O-p-cyanophenylthiophosphonate0,0-diethyl-O-2,4-dichlorophenylthiophosphate (DICHLORFENTHION)0,2,4-dichlorophenyl-O-methylisopropylamidothiophosphate0,0-diethyl-O-Z,5-dichloro-4-bromophenylthiophospate (BROMOPHOS-ETHYL)dimethyl-p-(methylthio)phenylphosphate0,0-dimethyl-O-p-sulphamidophenylthiophosphateO-[p-(p-chlorophenyl)azophenyl]0,0-dimethylthiophosphate (AZOTHOATE)O-ethyl-S-4-chlorophenyl-ethyldithiophosphateO-isobutyl-S-p-chlorophenyl-ethyldithiophosphate0,0-dimethyl-S-p-chlorophenylthiophosphate0,0-dimethyl-S-(p-chlorophenylthiomethyl)dithiophosphate0,0-diethyl-p-chlorophenylmercaptomethyldithiophosphate(CARBOPHENOTHION) 0,0-diethyl-S-p-chlorophenylthiomethylthiophosphate0,0-dimethyl-S-(carbethoxy-phenylmethyl)dithiophosphate (PHENTHOATE)0,0-diethyl-S-(carbofluorethoxy-phenylmethyl)- dithiophosphate0,0-dimethyl-S-carboisopropoxy-phenylmethyl)- dithiophosphate0,0-diethyl-7-hydroxy-3 ,4-tetramethylenecoumarinyl-thiophosphate(COUMITHOATE) 2-methoxy-4-H-1 ,3 ,2-benzodioxaphosphorin-2- sulphide0,0-diethyl-O-(5-phenyl-3-isooxazolyl)thiophosphate2-(diethoxyphosphinylimino)-4-methyl-l ,3-

dithiolane tris-( 2-methyll -aziridinyl)-phosphine oxide (METEPA)S-(2-chlor0-1-phthalimidoethyl-0,0-diethyldithiophosphateN-hydroxynaphthalimido-diethylphosphate (DlOCT- (MONI- thiophosphate 6dimethyl-3,5,6-trichloro-2-pyridylphosphate0,0-dimethyl-O-(3,5,6-trichloro-2-pyridyl)thiophosphateS-Z-(ethylsulphonyl)ethyl dimethylthiolphosphate (DlOXYDEMETON-S-METHYL)diethyl-S-Z-(ethylsulphinyl)ethyl dithiophosphate (OXIDISULFOTON)bis-0,0-diethylthiophosphoric acid anhydride (SUL- FOTEP) dimethyl-l,3-di(carbomethoxy)- l -propen-2-ylphosphatedimethyl(2,2,2-trichloro-l-butyroyloxyethyl)phosphate (BUTONATE)0,0-dimethyl-O-(2,2-dichloro-l-methoxyvinyl)phosphatebis(dimethylamido)fluorphosphate (DIMEFOX)3,4-dichlorobenzyl-triphenylphosphoniumchloridedimethyl-N-methoxymethylcarbamoylmethyldithiophosphate (FORMOCARBAM)0,0-diethyl-O-( 2,2-dichlorol -chloroethoxyvinyl)- phosphate0,0-dimethyl-O-( 2,2-dichlorol -chloroethoxyvinyl)phosphateO-ethyl-S,S-diphenyldithiolphosphateO-ethyl-S-benzyl-phenyldithiophosphonate0,0-diethyl-S-benzyl-thiolphosphate0,0-dimethyl-S-(4-chlorophenylthiomethyl)dithiophosphate(METHYLCARBOPHENOTHION) 0,0-dimethyl-S-(ethylthiomethyl)dithiophosphatediisopropylaminofluorophosphate (MIPAFOX)0,0-dimethyl-S-(morpholinylcarbamoylmethyl)dithiophosphate (MORPHOTHION)bismethylamido-phenylphosphate0,0-dimethyl-S-(benzenesulphonyl)dithiophosphate 0,0-dimethyl-(S andO)-ethylsulphinylethylthiophosphate 0,0-diethyl-O-4-nitrophenylphosphatetriethoxy-isopropoxy-bis( thiophosphinyl )disulphide2-methoxy-4l-l-1,3,2-benzodioxaphosphorin-Z-oxideoctamethylpyrophosphoramide (SCHRADAN) bis-( dimethoxythiophosphinylsulphido phenylmethaneN,N,N',N'-tetramethyldiamidofluorophosphate (DIMEFOX)O-phenyl-O-p-nitrophenyl-methanethiophosphonate (COLEP)O-methyl-O-(2-chloro-4-tert.butyl-phenyl)-N- methylamidothiophosphate(NARLENE) O-ethyl-O-(2,4-dichlorophenyl)-phenylthiophosphonate0,0-diethyl-O-(4-methylmercapto-3,5-

dimethylphenyl)-thiophosphate4,4-bis-(0,0-dimethylthiophosphoryloxy)-diphenyl disulphide0,0-di-(B-chloroethyl-O-(3-chloro-4-methylcoum arinyl-7 )-phosphate S-(l-phthalimidoethyl)-0,0-diethyldithiophosphate0,0-dimethyl-O-(3-chloro-4- diethylsulphamylphenyl)-thiophosphateO-methyl-O-(2-carbisopropoxyphenyl)-amidothiophosphate5-(0,0-dimethylphosphoryl)-6-chlorobicyclo(3.2.0)-heptadiene( 1,5)O-methyl-O-( 2-i-propoxycarbonyll -methylvinyl ethylamidothiophosphate.

Nitrophenols and Derivatives 4,6-dinitro-6-rhethylphenol, sodium salt[Dinitrocresol] 5-methyl-2-methylcarbamoyloximinol ,3-

oxythiolane 2-( l-methoxy-Z-propoxy )phenyl-N- methylcarba'mate 2-(l-butin-3-yl-oxy)phenyl-N-methylearbamate l-dimethylcarbamyl-l-methylthio-O-methylcarbamyl-formoxime l-(2'-cyanoethylthio-O-methylcarbamylacetaldoximeO-methylcarbamyl-acetaldoxime l-methylthio-O-carbamyl-acetaldoxime O-(3-sec.butylphenyl )-N-phenylthio-N- methylcarbamate 2,5-dimethyl-l,3-dithiolane-2-( O-methylcarbamylaldoxime)O-Z-diphenyl-N-methylcarbamate2-(N-methylcarbamyl-oximino)-3-chlorobicyclo[2.2.l ]heptane2-(N-methylcarbamyl-oximino)- bicyclo[2.2.1]heptane3-isopropylphenyl-N-methyl-N-chloroacetalcarbamate3-isopropylphenyl-N-methyl-N-methylthiomethylcarbamateO-(2,2-dimethyl-4-chloro-2,3-dihydro-7 benzofu ranyl)-N-methyl-earbamate O-( 2,2,4-trimethyl-2,3dihydro-7-benzofuranyl )-Nmethylcarbamate O-naphthyl-N-methyl-N-acetal-carbamate0-5,6,7,8-tetrahydronaphthyl-N-methyl-carbamate3-isopropyl-4-methylthio-phenyl-N- methylcarbamate3,S-dimethyl-4-methoxy-phenyl-N-methylcarbamate3-methoxymethoxy-phenyl-N-methylcarbamate3-allyloxyphenyl-N-methylcarbamate2-propargyloxymethoxy-phenyl-N-methyl-carbamate2-allyloxyphenyl-N-methyl-carbamate4-methoxycarbonylamino-3isopropylphenyl-N- methyl-carbamate3,5-dimethyl-4-methoxycarbonylamino-phenyl-N- methyl-carbamate2'y-methylthiopropylphenyl-N-methyl-carbamate 3-(a-methoxymethyl-Z-propenyl )-phenyl-N-methylcarbamate2-chloro-5-tert.-butyl-phenyl-N-methyl-carbamate4-(methyl-propargylamino-3,S-xylyl-N-methylcarbamate4-(methyl-y-chloroallylamino)-3,5-xylyl-N-methylcarbamate 4-(methyl-B-chloroallylamino)-3.5-xylyl-N-methylcarbamate l-(B-ethoxycarbonylethyl )-3-methyl'5 -pyrazolyl- N,N-dimethylcarbamate3-methyl-4-(dimethylamino-methylmercaptomethyleneimino)phenyl-N-methylcarbamatel,3-bis( carbamoylthio )-2-(N,N-dimethylamino propanehydrochloride5,S-dimethylhydroresorcinoldimethylcarbamate2-[ethyl-propargylamino]-phenyl-N- methylcarbamate2-[methyl-propargylamino]-phenyl-N- methylcarbamate4-[dipropargylamino]-3-tolyl-N-methylcarbamate4-[diproparglyamino1-3,5-xylyl-N-methylcarbamate2-[allyl-isopropylamino]-phenyl-N-methylcarbamate3-[allyl-isopropylamino]-phenyl-N-methylcarbamate ChlorinatedHydrocarbons y-hexachlorocyclohexane [GAMMEXANE; LlN- DAN; y HC H]l,2,4,5,6,7,8,8-octachloro-3a,4,7,7a'tetrahydro-4,7-

methylene indane [CHLORDAN]l,4,5,6,7,8,8-heptachloro,3a,4,7,7a-tetrahydro- 4,7mcthylene indane[HEPTACHLOR] l,2,3,4,10,10-hexachloro-l,4,4a,5,8,8a-hexahydroendo-l,4-exo-5,8-dimethanonaphthalene [AL- DRIN] l,2,3,4,10,l0-hexachloro-6,7-epoxyl.4,4a,5 ,6,7,8,8a-octahydro-exol,4,endo-5,8- dimethanonaphthalene [DlFLORlN] 1 ,2,3,4, 10,10-hexachloro-5,7-epoxyl,4,4a,5 ,6,7,8,8a-octyhydro-endo-endo-S,8dimethanonaphthalene [ENDRIN] In addition to the properties citedhereinabove, the compounds of the formula I also exhibit activityagainst representatives of the division Thallophyta. But they are alsoactive against fungi, for example against the phytopathogenic fungibelonging to the following classes: Oomycetes, Zygomycetes, Ascomycetes,Basidiomycetes, Denteromycetes. The compounds of the formula l are alsosuitable for combating plant pathogenic nematodes.

The compounds of the formula I may be used as pure active substance ortogether with suitable carriers and- /or additives. Suitable carriersand additives can be solid or liquid and correspond to the substancesconventionally used in formulation technique such, for example, assolvents, dispersants, wetting agents, adhesives, thickeners, bindersand/or fertilisers.

For application, the compounds of the formula I may be processed todusts, emulsion concentrates, granules, dispersions, sprays, tosolutions, or suspensions, in the conventional formulation which iscommonly employed in application technology. Mention may also be made ofcattle dips and spray races, in which aqueous preparations are used.

The agents according to the invention are manufactured in known mannerby intimately mixing and/or grinding active substances of the formula Iwith the suitable carriers, optionally with the addition of dispersantsor solvents which are inert towards the active substances. The activesubstances may take, and be used in, the following forms.

Solid forms:

Dusts, tracking agents, granules, coated granules, impregnated granulesand homogeneous granules. Liquid forms:

a. active substances which are dispersible in water:

wettable powders, pasts, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the activesubstances are mixed with solid carriers. Suitable carriers are, forexample: kaolin, talcum, bolus, loess, chalk, limestone, groundlimestone, attaclay. dolomite, diatomaceous earth, precipitated silica,alkaline earth silicates, sodium and potassium aluminium silicates(feldspar and mica), calcium and magnesium sulphates, magnesium oxide,ground synthetic materials, fertilisers, for example ammonium sulphate,ammonium phosphate, ammonium nitrate, urea, ground vegetable products,such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,residues of plant extractions, activated charcoal etc. These substancescan either be used singly or in admixture with one another.

Granules can be very easily manufactured by dissolving an activesubstance of the formula 1 in an organic solvent and applying theresulting solution to a granulated material, for example attapulgite,SlO

granicalcium, bentonite, etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the activesubstances of the formula I with polymerisable compounds(urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde orothers), whereupon a mild polymerisation is carried out that does notaffect the active substances and in the process of which the granulationis carried out during the gel formation. It is more advantageous toimpregnate finished, porous polymer granules (urea/formaldehyde,polyacrylonitrile, polyester or others) which have a specific surfacearea and a favourable predeterminable adsorption/desorption ratio, withthe active substances, for example in the form of their solutions (in alow boiling solvent) and to remove the solvent. Polymer granules of thiskind in the form of microgranules having a bulk density of 300 g/literto 600 g/liter can also be manufactured with the aid of atomisers. Thedusting can be carried out from aircraft over extensive areas ofcultures of useful plants.

It is also possible to obtain granules by compacting the carier with theactive substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilise the activesubstance and/or non-ionic, anionic and cationic surface activesubstances, which, for example, improve the adhesion of the activeingredients on plants or parts of plants (adhesives and agglutinants)and/or ensure a better wettability (wetting agents) and dispersibility(dispersing agents). Examples of suitable adhesives are the following:olein/chalk mixture, cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having to ethylene oxide radicals per molecule and 8 to9 carbon atoms in the alkyl radical, lignin sulphonic acids, theiralkali metal and alkaline earth metal salts, polyethylene glycol ethers(carbowaxes), fatty alcohol polyethylene glycol ethers having 5 toethylene oxide radicals per molecule and 8 to 18 carbon atoms in thefatty alcohol moiety, condensation products of ethylene oxide/ propyleneoxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation productsof urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e.wettable powders, pastes and emulsifiable concentrates, are agents whichcan be diluted with water to any concentration desired. They consist ofactive substance, carrier, optionally additives which stabilise theactive substance, surface-active substance and anti-foam agents and,optionally, solvents.

Wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Suitable carriers are,for example, those mentioned for the solid forms of application. In somecases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulphonated napthalene and sulphonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulphonic acids with phenol and form aldehyde, as well as alkali,ammonium and alkaline earth metal salts of lignin sulphonic acid, inaddition, alkylaryl sulphonates, alkali and alkaline earth metal saltsof dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such assalts of sulphated hexadecanols, heptadecanols, octadecanols, and saltsof sulphated fatty alcohol glycol ethers, the sodium salt of oleoylethionate, the sodium salts of oleoyl methyl tauride, ditertiaryacetylene glycols, dialkyl dilauryl ammonium chloride and fatty acidalkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

The active substances are mixed, ground, sieved and strained with theadditives cited hereinabove in such a manner that, the size of the solidparticles does not exceed 0.02 to 0.04 p. in wettable powders, and 0.03p. in pastes. To produce emulsifiable concentrates and pastes,dispersing agents such as those cited above, organic solvents, and waterare used. Examples of suitable solvents are: alcohols, benzene, xylene,toluene, dimethyl sulphoxide, and mineral oil fractions which boilbetween 120 and 350C. The solvents must be practically odourless, notphytotoxic, and inert to the active substances.

Furthermore, the agents according to the invention can be applied in theform of solutions. For this purpose the active substances, or severalactive substances of the general formula 1, are dissolved in suitableorganic solvents, mixtures of solvents or in water. Aliphatic andaromatic hydrocarbons, chlorinated derivatives thereof, alkylnaphthalenes, and mineral oils, singly or in admixture with each other,can be used as organic solvents.

The content of active substance in the above described agents is between0.1% to 95%, in which connection it should be mentioned that, in thecase of application from aircraft or some other suitable means ofapplication, it is possible to use concentrations of up to 99.5% or evenpure active substance.

The active substances of the formula 1 can, for example, be formulatedas follows:

Dusts The following substances are used to manufacture (a) a 5% and (b)a 2% dust:

a. 5 parts of active substance 95 parts of talcum b. 2 parts of activesubstance 1 part of highly disperse silicic acid 97 parts of talcum.

The active substances are mixed with the carriers and ground.

Granules The following substances are used to produce 5% granules:

5 parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The thus obtained solution is sprayed on kaolin, and theacetone subsequently evaporated in vacuo.

Wettable powder:

The following constituents are used for the preparation of (a) a 40%,(b) and (c) a 25%, and (d) a 10% wettable powder:

lose mixture (1:2),

1.5 parts'of sodium dibutyl nate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalky 28.1 parts of kaolin.

c. 25 parts of active substance, i

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol,

1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), I

8.3 parts of sodium aluminium silicate,

16.5 parts of kieselguhr,

46 parts of kaolin.

d. parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of 'naphthalenesulphonic acid/formaldehyde condensate,

82 parts of kaolin. Y

The active substances are intimately mixed, in suitable mixers, with theadditives, the mixture being then ground in the appropriate mills .androllers. Wettable powders are obtained which can be diluted with waterto give suspensions of any desired concentration. Emulsifiableconcentrates:

The following substances are used to produce (a) a 10% and (b) a 25%emulsifiable concentrate:

a. 10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcoholpolyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene.

b. 25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an a1kylarylsulphonate/fatty alcoholpolyglycol ether mixture5 parts of dimethylformamide,

57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution withwater, emulsions of any desired concentration.

Spray:

The following constituents are used to prepare a 5% spray:

5 parts of active substance,

1 part of epichlorohydrin,

94 parts of benzine (boiling limits 160l90C).

EXAMPLE 1 O-ethyl-S-n-buty1-S-( 3 ,4-dihydro-4- l,2,3-benzotriazinon-3-yl methyl )-dithiophosphate "naphthalene sulphol1.3 g of N-chloromethylbenzazimide and g of the, potassium salt ofO-ethyl-S-n-butyldithiophosphoric acid are suspended in 100 ml ofacetone at room temperature. The reaction mixture is stirred for 1 hourat room temperature and for 5 hours at 5502 it is then cooled andstirred with 300 ml of ice water. The precipitated oil is taken up in100 ml of benzene. The benzene layer is separated, washed with 3% Na COsolution and with water and subsequently dried with sodium sulphate. Thebenzene is distilled off to leave as residue 15 g of an oil product witha refractive index of m, 1.5819; 11 1.5817.

calculated 7: P 8.3

The following compounds are manufactured in analogous manner:

CH3 N EXAMPLE 2 Insecticidal Ingest Poison Action Cotton plants weresprayed with a 0.05% aqueous active substance emulsion (obtained from a10% emulsifiable concentrate).

After the spray coating had dried, the cotton plants were populated withSpodoptera littoralis or Heliothis virescens larvae (L The test wascarried out at 24C and 60% relative humidity.

In the above test, the compounds according to Example 1 displayed goodinsecticidal ingest poison action against Spodoptera and l-leliothislarvae.

EXAMPLE 3 Action Against Chilo Suppressolis Six rice plants at a time ofthe variety Caloro were transplanted in plastic pots (diameter at thetop 17 cm) and reared to a height of about 60 cm. Infestation with Chilosuppressalis larvae (L 3-4 mm in length) took place 2 days after theactive substance had been applied in granule form to the paddy water(rate of application: 8 kg of active substance per hectare). Evaluationof the insecticidal action ensued 10 days after application of thegranules.

1n the above test, the compounds according to Example I acted againstChilo suppressalis.

EXAMPLE 4 Action Against Ticks A. Rhipicephalus bursa Five adult ticksor 50 ticks larvae were counted into a test tube and immersed for l to 2minutes in 2 ml of an aqueous emulsion series each containing 100, 10, l

and 0.1 ppm of test substance. The tube was then sealed with astandardised cotton wool plug and stood on its head so as to enable thecotton wool to absorb the active substance emulsion.

In the case of the adults evaluation took place after 2 weeks, and inthat of the larvae after 2 days. Each test was repeated twice.

B. Boophilus microplus (larvae) Tests were carried out with sensitiveand 20 OP resistant larvae with a dilution series analogous to that usedin test A. (The resistance refers to the tolerability of diazinon).

In these tests, the compounds according to Example I acted againstadults and larvae of Rhipicephalus bursa and sensitive and OP-resistantlarvae of Boophilus microplus. 7

EXAMPLE 5 Acaricidal Action Phaseolus vulgaris (plants) were overlaidwith an infested piece of leaf from a mass culture of Tetranychusurticae l2 hours before the test for acaricidal action. The mobilestages which had spread over the plants were sprayed with the emulsifiedtest preparations from a chromatography atomiser so that the spray brothdid not run off. The number of living and dead larvae, adults and eggswere evaluated ater 2 to 7 days under a stereoscopic microscope and theresult was expressed in percentages. During the interim, the treatedplants were kept in greenhouse compartments at C.

In the above test, the compounds according to Example I acted againstadults larvae and eggs of Tetranychus urticae.

EXAMPLE 6 Action Against Soil Nematodes To test the action against soilnematodes, the active substances were applied to, and intimately mixedwith, soil infected with root gall nematodes (Meloidgyne arenaria), inthe specifically indicated concentrations. Immediately afterwards,tomato cuttings were planted in the thus prepared soil in a series oftests, and after a waiting time of 8 days tomato seeds were sown inanother test series.

LII

wherein R, represents propyl, isopropyl, n-butyl, isobutyl or sec.butyl,and R represents methyl or ethyl.

2. The compound according to claim 1 of the formula 0 ll (n)C H S C Is-cu ls c a 0 3. The compound according to claim 1 of the formula 4. Thecompound according to claim 1 of the formula

1. A COMPOUND OF THE FORMULA